Nitro derivatives of substituted benzoates



Patented Mar. 2, 1954 NITRO DERIVATIVES or SUBSTITUTED V BENZOATES Arnold N. Johnson,

Terre Haute, Ind., assignor to Commercial Solvents Corporation, Ind., a corporation of Maryland Terre Haute,

No Drawing. Application February 27, 1952, Serial No. 273,765

" eoiaims. o1. zeo-rzsy My invention relates to new compositions of matter, more particularly to the nitro derivatives of substituted benzoates having the general formula:

wherein X is selected--from thegroup consisting of hydrogen, chlorine and bromine, Y is selected from the group consisting of hydrogen, methyl, chlorine and-bromine andR is selected from the group consisting of methyl and ethyl.

My new compositions of matter are produced by reacting a substituted nitro alcohol with substituted or unsubstituted benzoyl chloride at from C. to 150 0., ma suitable inert solvent, the upper limit of temperaturebeing set by the boiling point of the'solvent used for the reaction mixture.

Nitro alcohols which can be used to produce my new compounds are the Z-nitropropanols and 2-nitrobutanols carrying as Substituents at the 1 position a phenyl, tolyl, or halogenated phenyl group, such as l-phenyl-2-nitro-1-butanol, l-pchlorophenyl 2 nitro- 1 butanol, 1 ptolyl 2 nitro'- '1- butanol, 1 p L chlorophenyl 2 -nitro 1 propanol, 1 o chlorophenyl 2 nitro 1 butanol, 1 p bromophenyl 2 nitro 1 butanol, 1 o bromophenyl 2 nitro 1 butanol, 1 p bromophenyl 2 nitro 1 propanol, and 1 obromophenyl 2 nitro 1 propanol. The benzoates can be formed by reacting benzoyl chloride or a halogen substituted benzoyl chloride such as chlorobenzoyl chloride or bromobenzoyl chloride with the desired substituted nitro alcohol. Examples of benzoates thus formed are: 1- phenyl-2-nitrobutyl p-chlorobenzoate, l-phenyl- 2-nitrobutyl o-chlorobenzoate, l-p-chlorophenyl- 2-nitrobuty1 o-chlorobenzoate, 1-p-chl0ropheny1- 2-nitrobutyl p-chlorobenzoate, 1-p-tolyl-2-nitrobutyl benzoate, 1-p-chlorophenyl-2-nitropropyl benzoate, 1 p bromophenyl 2 nitrobutyl p bromobenzoate, 1 p bromophenyl 2- nitropropyl o bromobenzoate, 1 p bromophenyl 2 nitrobutyl o chlorobenzoate, 1- p bromophenyl 2 nitropropyl p chlorobenzoate, etc. Pyridine or other basic diluents such as quinoline may be used as solvents and reagents to take up the hydrogen chloride formed, or an inert solvent such as benzene, cyclohexane, or n-heptane may be used and the hydrogen chloride evolved vented to the atmosphere or absorbed in a water scrubber.

wise the o The several nitroalcohols employed as starting materials can be prepared in the following manner. 7 The 1-pheny1 2-nitro-l-butanol is prepared by agitating a mixture of excess l-nitropropane and 1 mole of benzaldehyde for 3 hours atv from 20 to 50 C. after the slow addition of t; mole of 3.2 normal alcoholic potassium hydroxide. The mixture is then acidified with mineral acid to a pH of about 2. Excess l-nitropropaneis then, removed by steam distillation to a vapor temperature of 99 C. at which point the distillate is essentially water. If the pH is much above 2, appreciable benzaldehyde appears in the steam distillate and lowers the yield of l-phenyl- 2-nitro-1-butano1.

The 1' o and p chlorophenyl 2 nitrol-butanols, 1-0 and p-bromophenyl-2-nitro-1- butanols, and 1-0 and p-tolyl-2-nitro-1-butanols are. prepared by the same procedure as that outlined above for 1'-phenyl-2-nitro -1-butanol except that o or p-chlorobenzaldehyde, 0 or p: bromobenzalclehyde, and 0 .or p-methylbenzaldehyde (o'or p-toluic aldehyde) are substituted for the benzaldehyde utilized in the first step. Likeand p-chlorophenyl-Z-nitro-l-propanois and o and p-bromophenyl-2-nitro-l-propanolsare prepared by the same procedure exceptthat nitroethane is substituted in place of the l-nitropropane of the first step. i

The following examples are ofiered to illustrate my invention and it is not intended that my invention be construed as limited to the ratios, amounts or specific compounds shown therein.

Example I The l-phenyl-2-nitrobutyl p-chlorobenzoate of my invention was prepared as follows: in 100 ml. of pyridine was mixed 19.5 gm. of 1-phenyl-2- nitro-l-butanol and 19 gm. of p-chlorobenzoyl chloride and the esterification reaction between the nitro alcohol and the p-chlorobenzoyl chloride was allowed to proceed 4 hours at room temperature. Two hundred fifty ml. of water and 100 ml. of 50% acetic acid were then added and the solution decanted from an oil residue. The solution was extracted with 100 ml. chloroform and the extract added to the yellow oil. One hundred ml. of chloroform were added to the oil and extract mixture and said mixture was washed with 50% acetic acid, water, and 5% sodium carbonate and dried with anhydrous sodium sulfate. The mixture was then concentrated to ml. and filtered, discarding the insoluble material. To the filtrate was then added ml. of ligroin, the mixture cooled, and the insoluble rine against calculated values .of 430% nitrogen: The. 3.7 a gun of crystals 7 and 10.63% chlorine. represented a yield of 11% based on the 19.5. gm:- of nitro alcohol.

Example II The l-p-chlorophenyl-2-nitrobutyl p-chlorobenzoate of my invention was preparedasi'bllows: to 100 ml. of benzene solvent was added 60.0 i gm. of lI-p-chlorophenyl-2 nitro-l '-butanol, 62.6gm; of p'-chlorobenzoyl chloride, and a mesh lump'of charcoal as'catalyst. The course of the l esterification was followed by absorbing the hydrogen-chloride evolved in a water scrub her. At 25. 7"hoursand at -hours 1 ml; of chlorosulfonic acid'was'added as catalyst; After l5liours ml. of benzene" were added and the mixture refluxed for" 3-- hours, then filtered. Thereafter the filtratewas' steam distilled and 725 grams of" semis'olidwere obtained as nonvolatile residue; A 45.3 gm; aliquot'ofthe crude semisolidwas-recrystallizedfrom ml; of ethyl alcohol-*and l816 gm: of'crystals' melting at 109 C. were obtained which represented'a'yield of 312493 based on the moles ofnitro alcohols used. The fi'rst cropof:'crysta ls' on analysis showed 19.29%--chlorine and-354% nitrogen against-the calculated values-oi l93'%'- chlorine and 3.8%- nitrogen. A second crop of"'0.7' gm. was not analyzed; Evaporation of' the ethanol gave a residue of 118-18 gm; which fraction probably contained 'appreciable amounts of the ester'sinceits analysis showed 20.25 trogens 'lf'h'isresidue was'not further purified;-

The' members of "this new series of compounds are-useful as --intermediates in I thesproduction of f insecticides: The members of the series-of compounds are themselves insecticides as eshownbythe results set forth in the .table below;

The table sets forth chlorine and 4.01% -nithe results 'of-"tests of l-- pheny1-2-nitrobuty1 p-chlorobenzoate and l-pchlorophenyl against Mexican bean beetles.

2 nitrobutyl p chlorobenzoate The testing procedure used was substantially as follows: A dust made up of a uniform mixture of the requisite amount-of the new compound togive the desired dilution? host plants ferred to these plants. the precentage of a'zsoli'd inertizcarrier was. applied to and the healthy insects then trans- At the end of 48 hours dead insects was determined and the amounts of the food plants consumed were'noted.

TABLE [lElMexlce-n bean-beetle larvae per dilution] 1 Percent No. Dead Percent Amt. Food Dilution (48 hours) Kill Consumed UntreatedObntrol 0 0 Large. 1-p-chlorcphenyl-2- nitrobutyl p-chlorobenzoatc; 1. 10 Piece, l-phenyl-tnitrobutyl p-chlorobenzoate. 1 10 100 Do.

Now having described my invention what I" claim is:

l. The compounds represented by the formula wherein. X1 isselected from the group consisting.

of hydrogen,

chlorine and bromine,. Y isrselected'.

benzoate.

: pound 1-p-chlor0plienyl 2 nitrObutyI p-clil'oro 4; As a new compositionroflmatter thecom: pound 1 p-tolyl2 nitrobutyljbenzoate.

SLAsanew composition of matter. the .com= pound l-p-chlOroplienyl-Zmitropropyl b'enzoata.

6. As a new composition of matter. thecom: poundj 1-peldromophenyl 2 nitrobutyl p-bromo benzoate.

ARNOLD N; JOHNSQN..' 

1. THE COMPOUNDS REPRESENTED BY THE FORMULA 